Host-Guest-Systems Based on Nanoporous Crystals

Host-Guest-Systems Based on Nanoporous Crystals......Page 4
Contents......Page 8
List of Contributors......Page 22
Part 1 Synthesis Routes for Functional Composites Based on Nanoporous Materials......Page 28
References......Page 33
1.1 Introduction......Page 34
1.3 Stable Functional Structure-Directing Agents in the Synthesis of Porosils......Page 37
1.4 The Glycol Method for the Fast Synthesis of Aluminophosphates and the Occlusion of Organic Dye Molecules......Page 45
1.5 Easily Crystallizing Inorganic Frameworks: Zincophosphates......Page 48
References......Page 52
2.1 Introduction......Page 56
2.2 In Situ Synthesis of Azo Dyes in Faujasites......Page 57
2.3 In Situ Synthesis of Spiropyran Dyes in Faujasites......Page 60
2.4 Optical Switching of Azo and a Spiropyran Dyes in Molecular Sieves......Page 63
References......Page 68
3.1 Introduction......Page 71
3.2 Dyes in the Microporous Molecular Sieve AlPO(4)-5......Page 72
3.2.1 Crystallization Inclusion of Dyes in AlPO(4)-5......Page 73
3.2.2 Crystal Morphology of AlPO(4)-5......Page 80
3.3 Dyes in the Mesoporous Molecular Sieve Si-MCM-41......Page 83
References......Page 87
4.1 Introduction......Page 91
4.1.1 Synthesis of Molecular Sieve Crystals of Tailored Dimensions and Habitus......Page 92
4.2.1 General Remarks and Synthesis Procedure......Page 93
4.2.3 Inorganic Salts of 2+ and Higher Valence Metal Ions as Additional Components......Page 94
4.2.4 Other Organic Templates as Additional Components and/or Co-Templates......Page 96
4.2.5 Organic Acids as Additional Components and Co-Templates......Page 97
4.2.7 Mixed Organic/Inorganic Additional Components as Co-Templates......Page 99
4.2.8 Aluminum Source as Directing Agent......Page 101
4.2.9 Preparation of the Reaction Gel as a Control Tool......Page 102
4.2.10 Sorption Characteristics of the Tailored Crystals......Page 103
4.3 Conclusions......Page 105
References......Page 108
5.1 Introduction......Page 111
5.2 Liquid Crystals Confined in Molecular Sieves......Page 112
5.3 Methods of Loading Molecular Sieves with Liquid Crystals......Page 113
5.4 Nanoporous Composites Based on Different Molecular Sieves......Page 115
5.4.1 MFI Type Molecular Sieves......Page 116
5.4.2 Faujasite......Page 117
5.4.3 Cloverite......Page 119
5.4.4 MCM-41 Molecular Sieves......Page 120
5.4.5 SBA-15 Materials......Page 122
5.4.6 Exchanged Nanoporous Materials......Page 124
5.5 On the Location of Liquid Crystals Inside the Pores or Cavities of Molecular Sieves......Page 125
5.6 Conclusions......Page 127
References......Page 128
6.1 Introduction......Page 130
6.2 Concept......Page 132
6.3 Results and Discussion......Page 134
References......Page 145
7.1 Introduction......Page 148
7.2 Mesostructured Composites of Azobenzene Surfactants and Silica......Page 152
7.2.1 Synthesis and Structural Characterization of Azobenzene Surfactants in the Synthesis of Silica Mesostructures......Page 153
7.2.2 Mesoporous Materials from Templating with Azobenzene Amphiphiles......Page 160
7.2.3 Photoisomerization in Azo Amphiphile–Silica Composites......Page 161
7.2.4 Chemical Switching of Azobenzene Surfactant–Silica Composites: Basis for a "Nanoscale Elevator"?......Page 163
Acknowledgements......Page 168
References......Page 169
8.1 Introduction......Page 172
8.2 Titanium Oxide Clusters......Page 173
8.2.1 Redox Properties......Page 177
8.3.1 Tin Oxide Nanoparticles in Zeolites......Page 179
8.3.2 Tin Oxide Clusters in Mesoporous Materials......Page 183
8.4 Vanadium Oxide Clusters......Page 186
8.4.1 Reduction and Re-oxidation......Page 187
8.5 Conclusions......Page 188
References......Page 189
9.1 Introduction......Page 192
9.2.1 Formation of Pt Carbonyls Monitored by FTIR, EXAFS, and UV/vis Spectroscopy......Page 193
9.3.1 Decomposition in Oxygen......Page 199
9.3.2 Decomposition in Vacuum......Page 200
9.4 Stable Subnanometer Platinum Clusters......Page 202
9.5 Electron Donor Properties of Pt Clusters Derived from Chini Complexes......Page 204
References......Page 207
10.1.2 Nanostructure......Page 210
10.1.4 Synthesis Conditions......Page 211
10.2 Inverse Hexagonal Mesostructured Aluminum Phosphates......Page 212
10.3 Tubular Mesoporous Aluminum Phosphates......Page 216
References......Page 222
11.1.1 Phosphates and Phosphonates: Structure and Intercalation......Page 224
11.1.2 Self-Assembly Technique......Page 226
11.1.3 Self-Assembly of Zirconium Phosphonates......Page 228
11.2.2 Synthesis of Bisphosphonates......Page 231
11.3.1 General......Page 232
11.3.3 Multilayer Formation......Page 233
11.3.5 Automatic Deposition......Page 236
11.4 Applications......Page 237
11.5 Conclusions......Page 240
References......Page 241
12.1 Introduction......Page 244
12.2 Guest-Free Homoleptic SPB Derivatives......Page 246
12.3 Guest-Free Heteroleptic systems......Page 247
12.4 Host-Guest Systems with Uncharged or Cationic Guests......Page 254
12.5 Truncated and Expanded SPB Derivatives......Page 259
12.6 Conclusions......Page 260
References......Page 263
Part 2 Structure and Dynamics of Guest–Host Composites Based on Nanoporous Crystals......Page 266
References......Page 270
1.2 Computational Problems in Host–Guest Chemistry and Physics......Page 271
1.3 Structure Predictions for Host–Guest Systems using Periodic Boundary Conditions......Page 272
1.4 Structure Predictions for Host–guest Systems Using Periodic Boundary Conditions......Page 274
1.5 Cluster Model Studies for Host–Guest Systems......Page 276
1.6 Electronic and Magnetic Properties of Host–Guest Systems......Page 278
References......Page 279
2.1 Introduction......Page 282
2.2 Principles of Interference Microscopy......Page 283
2.3 Transient Uptake in Zeolite LTA......Page 285
2.4 Evidence of Inner Transport Barriers in Zeolite MFI......Page 286
2.5.1 Peculiarities of One-Dimensional Diffusion and Options for its Observation......Page 291
2.5.2 Channel Accessibility in AFI-Type Crystals......Page 295
2.5.3 Transient Concentration Profiles in AFI-Type Zeolites......Page 299
2.5.4 Guest Distribution in Ferrierite......Page 301
2.6 Conclusions......Page 302
References......Page 303
3.1 Introduction......Page 307
3.2.1 High Resolution Synchrotron Radiation Powder Diffractometry......Page 309
3.2.2 Neutron Powder Diffraction......Page 311
3.2.3 High-Pressure Behavior......Page 314
3.3.1 Nuclear Magnetic Resonance Measurements......Page 316
3.3.2 Deep Inelastic Neutron Scattering......Page 319
3.4.1 Experiments Using a Normal-Pressure Flow Device......Page 320
3.4.2 Incorporation of Methanol into the Framework of γ-CaSO(4)......Page 324
3.5.2 Nuclear Magnetic Resonance Measurements......Page 325
3.6 Conclusions......Page 330
References......Page 331
4.1 Introduction......Page 333
4.2.1 Localization of Guest Molecules by Powder Diffraction......Page 334
4.3.1 TTF and TCNQ in Zeolite Faujasite NaY......Page 336
4.3.2 TTF and TCNQ in Zeolite Faujasite HY......Page 339
4.3.3 Naphthalene, Anthracene, 2,3-Benzanthracene, and Pentacene in NaY......Page 341
4.3.4 Chloranil in NaY......Page 346
4.4 Summary......Page 348
References......Page 349
5.1 Introduction......Page 351
5.2.1 Determination of Local Minima......Page 353
5.2.2 Classification of Minima......Page 355
5.2.3 Discrete State Approximation......Page 357
5.3.1 Structural Properties......Page 358
5.3.2 Energetics......Page 361
5.4 Summary and Conclusions......Page 363
Acknowledgements......Page 364
References......Page 365
6.1 Introduction......Page 366
6.2.1 Location of Cations......Page 367
6.2.1.1 Alkali Cations......Page 368
6.2.1.3 Rhodium Cation......Page 369
6.2.2.1 Basicity......Page 370
6.2.2.2 Brønsted Acidity......Page 371
6.2.3.1 Carbon Monoxide......Page 373
6.2.3.2 Nitrogen Molecule......Page 375
6.2.3.3 Methane......Page 376
6.2.3.4 Methanol......Page 377
6.3.1.2 Pt(4) clusters......Page 378
6.3.2 Structure of Metal Clusters in Zeolite Cages: Case Study of Ir(4)......Page 379
References......Page 382
Part 3 Electrical Properties and Electronic Structure......Page 386
References......Page 390
1.1 Introduction: Historical Survey of Metal Cation Conduction in Dehydrated Zeolites......Page 391
1.2 Proton Conduction......Page 393
1.2.1 Impedance Measurements on Dehydrated H-ZSM-5......Page 394
1.2.2 Quantum Chemical Description of Translational Proton Motion in H-ZSM-5......Page 396
1.2.3 Effect of Guest Molecules on Proton Mobility......Page 398
1.3 Application of H-ZSM-5 as NH(3) Sensor for SCR Applications......Page 399
1.4 Summary......Page 402
References......Page 403
2.2 Ethylene Glycol in Zeolites......Page 406
2.4 Poly(Vinyl Ether) in Mesoporous MCMs......Page 413
2.5 Conclusions......Page 417
References......Page 419
3.1.1 Molecular Electronics......Page 420
3.1.2 Mesoporous Materials......Page 421
3.2 Metal Nanowires and Nanoarrays in Mesoporous Hosts......Page 422
3.3 Semiconductor Nanoparticles and Nanoarrays in Mesoporous Hosts......Page 426
3.4 Carbon Nanotubes and Graphitic Filaments in Host Materials......Page 430
References......Page 433
4.1 Introduction......Page 437
4.2 Theory......Page 440
4.3 Magnetic Ordering and Heisenberg Coupling Constants......Page 443
4.4 Spin Density Distribution......Page 445
4.5 Paramagnetic NMR Shifts for (27)Al and (29)Si Framework Nuclei......Page 446
4.6 Concluding Comment......Page 448
References......Page 449
5.1 Introduction......Page 451
5.2 H(8)Si(8)O(12): A Model for the Vibrational and Electronic Structure of Zeolite A......Page 452
5.3 Electronic Structure of Cu(+)-, Ag(+)-, and Au(+)-Loaded Zeolites......Page 455
5.4 Electronic Structure of Ag(+)-Zeolite A......Page 457
5.5 Quantum-Sized Silver Sulfide Clusters in Zeolite A......Page 462
5.6 Intrazeolite Charge Transport......Page 467
5.7 Conclusions......Page 473
References......Page 475
6.1 Introduction......Page 478
6.2 Synthesis and Structure......Page 479
6.3 Experimental Setups......Page 481
6.4 The Augmented Fourier Component Method: Computational Details......Page 484
6.5.1 Density of States......Page 486
6.5.2 Band Structure......Page 489
6.5.4 Anisotropy of the Electrical Conductivity......Page 491
6.5.5 Electron Density......Page 496
6.5.6 Cetineite Mixed Phases......Page 498
6.5.7 Host/Guest-Interaction of (K;Se)......Page 500
6.6 Conclusions......Page 502
References......Page 503
Part 4 Optical Properties of Molecular Sieve Compounds......Page 506
References......Page 510
1.2 Switchable Natural and Technical Membranes......Page 511
1.2.1 Realized Switchable Membrane Systems......Page 512
1.3 Characterization of Used Host–Guest Systems......Page 513
1.3.1 Monte Carlo Simulations of the Free Pore Volume in the Host–Guest Systems MFI–AZB and FAU–AZB......Page 515
1.3.2 Reversible Photoinduced Azobenzene Isomerization in the Host–Guest Systems MFI–AZB and FAU–AZB......Page 517
1.3.3 Preparation and Irradiation of FAU-AZB and MFI-AZB Membranes......Page 518
1.4 Results and Discussion......Page 520
1.4.1 Switchable Single-Gas Permeance Across MFI–AZB and FAU–AZB Membranes......Page 521
1.4.2 Switchable Gas-Mixture Permeance across the NaX Membrane......Page 524
1.5 Summary......Page 525
References......Page 526
2.1 Introduction......Page 528
2.2.1 Alignment of Guest Molecules......Page 529
2.2.3 Birefringence of Nanocomposites......Page 531
2.2.4 UV/Vis Spectroscopic Properties of Zeolite-Encapsulated Guest Molecules......Page 532
2.3.1 Photochromism......Page 534
2.3.2 Photosensitive Refractive Index Switching......Page 536
2.3.3.1 Influence of the Host on Stability of Switching States, Dynamic Range, Sensitivity, and Reversibility......Page 538
2.3.3.2 Influence of the Guest on Optimum Excitation Wavelength, Stability of Switching States, and Dynamic Range......Page 541
2.4 Summary......Page 544
References......Page 545
3.1 Introduction......Page 548
3.2 Confocal Microscopy......Page 550
3.3.1.1 Staining Defect Structures in Silicalite-1 (MFI)......Page 554
3.3.1.2 Staining Defect Structures in AlPO(4)-5 (AFI)......Page 558
3.3.1.3 Staining During Synthesis: DCM in AlPO(4)-5 (AFI)......Page 560
3.3.2 Observation of Diffusion......Page 561
3.3.3 Stilbene Derivative in AlPO(4)-5 (AFI)......Page 563
3.3.4 Terrylene in MCM-48 and MCM-50......Page 564
3.3.5 Single Molecules: Perspectives......Page 565
3.4 Conclusion......Page 568
References......Page 569
4.2 Host–Guest Composites based on Molecular Sieves......Page 571
4.3 Microporous Aluminophosphates......Page 572
4.3.1 Synthesis of Large, Perfect AlPO(4)-5 Crystals......Page 573
4.4 Single-Crystal Microlasers......Page 574
4.4.1 Morphology of AlPO(4)-5/Laser Dye Crystals......Page 575
4.4.2 Optical Properties of Laser Dyes in AlPO(4)-5......Page 576
4.4.3 Dye-Loading Profiles......Page 578
4.4.4 Laser Activity in AlPO(4)-5/Dye Crystals......Page 580
4.5 Outlook......Page 581
References......Page 582
5.1 Introduction, Motivation, and Scope......Page 585
5.2 Synopsis......Page 587
5.3.1 Preparative Aspects......Page 591
5.3.2 Effects of Doping Levels and Location in the Zeolite......Page 593
5.3.3.1 Salicylates......Page 594
5.3.3.2 Picolinates......Page 596
5.3.3.3 Thenyltrifluoroacteylacetonates......Page 597
5.3.3.4 Comparison of Ligands......Page 600
5.3.4.1 Energy Transfer between Free and Complexing Ligands (L(γ) —> L(Ln3+))......Page 601
5.3.4.3 Ln(3+) —> Ln(3+) and Energy Transfer between Complexing Ligands (L(Ln3+) —> L(Ln3+))......Page 602
5.3.5 Size......Page 605
5.3.6 Surface Efficiency......Page 607
References......Page 608
6.1 Introduction......Page 611
6.2.1 Organic Dyes as Laser Gain Medium......Page 612
6.2.3 Crystal Morphology......Page 614
6.2.4 Dye Molecule Alignment and Pyroelectric Material Properties......Page 615
6.3.1 Absorption, Dichroism, and Birefringence......Page 616
6.3.2.1 Fluorescence Spectra......Page 618
6.3.2.2 Spontaneous Emission Dynamics......Page 620
6.4 Laser Properties......Page 624
6.4.2 Temporal Coherence of the Laser Emission......Page 625
6.4.3 Spatial Coherence of the Laser Emission......Page 626
6.4.4 Laser Threshold and Differential Efficiency......Page 628
6.4.5.1 The Ray Picture of The Hexagonal Resonator......Page 630
6.4.5.2 The Wave Picture......Page 631
6.5 Photostability......Page 636
6.5.1 Model of the Photostability Kinetics......Page 637
References......Page 643
7.1 Introduction......Page 645
7.2.1 Mesoporous Systems Useful for Optical Materials......Page 646
7.2.2 Mesopore Environment......Page 647
7.2.3 Fiber Synthesis......Page 648
7.2.4 Internal Structure......Page 649
7.2.5 Morphology Control and Hierarchical Structures......Page 650
7.3 Optically Amplifying Materials Based on Mesostructured Systems......Page 652
7.4.1 Priciples of Laser Design......Page 653
7.4.3 Spectroscopic Properties......Page 655
7.4.4 Threshold Behavior......Page 657
References......Page 658
8.1 Introduction......Page 660
8.2.1.1 Bulk Samples......Page 661
8.2.2.2 Layers......Page 662
8.2.3.3 Transparency of Composites......Page 663
8.3.1.1 Zeolites......Page 664
8.3.1.2 Copolymers......Page 665
8.3.1.3 Bulk Composites......Page 668
8.3.1.4 Composite Layers......Page 670
8.4.1 Procedures......Page 672
Acknowledgements......Page 673
References......Page 674
Index......Page 676